Process for Producing Highly Activated Electrode Through Electro-Activation

ABSTRACT

A method for treating a carbonaceous biochar electrode with an applied electric potential and resulting electric current, while submerged in an electrolyte, is disclosed in order to increase the biochar electrode&#39;s pore surface area and pore hierarchy, to affect a cleaning of unwanted materials and compounds from within the electrode and to optionally plate materials onto the surface pores of the electrode, such as graphene or metals, thus increasing the energy storage capacity of the biochar electrode when used in an energy storage device. Exemplary applications include electrodes for ultra-capacitors, pseudo-capacitors, batteries, fuel cells and other absorbing and desorbing applications.

CROSS-REFERENCE TO RELATED APPLICATION

The present application is a continuation application that claims the benefit of a PCT patent application, PCT/US2020/025648, filed Mar. 30, 2020, which in turn claimed the benefit of a provisional patent application entitled “Process for Producing Highly Activated Electrode Through Electro-Activation,” which was filed on Mar. 29, 2019, and assigned Ser. No. 62/826,038. The subject matter of each of the foregoing applications is herein incorporated by reference in its entirety.

BACKGROUND Technical Field

The present disclosure describes a method of treatment of an electrode material with an applied electrical potential and electric current, to induce electrolysis treatment of the electrode.

Background Art

As alternative energy, renewable energy and electric cars grow more and more popular, existing energy storage technology is inadequate and will continue to fall short of meeting the growing demand for absorbing, storing and rapidly delivering of electrical energy unless a new energy storage solution is found. A major focus has been on lithium-based chemistry for rechargeable batteries. These batteries involve chemical reactions to store electric power. The reactions are slow and generate heat, which causes inherent loss of energy. In most battery embodiments, one electrode has significant carbon makeup. The other electrode's potency is a function of its surface area and pore volume that therein provides molecular sites for the electrochemical reaction and hence for electric charge energy storage to occur.

Ultra-capacitors store electrical energy by an electrostatic mechanism, not a chemical reaction as found in batteries. Therefore, the electric charge storage mechanism in ultra-capacitors is not rate-limited by a chemical reaction. The superior charge storage capability of ultra-capacitors is a function of pore volume and surface area. The energy storage mechanism of ultra-capacitors via transport of ions and attraction to the charge storage sites on the electrodes is limited in the existing technology because of the electrode morphology applied to the supporting members (foils, membranes, separators, etc.) that form “packaging overhead” in the overall ultra-capacitor device assembly for the given amount of electrode material. Limitations of that electrode layer in existing ultra-capacitor technology are founded in either the thickness of the electrode as it resides between the charge collector metal foil and the non-conductive separator membrane, as well and the total surface area within the channels, walls and pores of the electrode.

These electrodes are generally fabricated from electrically conductive activated carbon. Other materials for the electrode apply highly scientific and costly engineered materials such as carbon nanotubes, fullerenes, “Bucky-Balls” and other such mesh-like and web-like molecular structures, to increase the available surface area within the pores, walls and channels of the electrode.

Although ultra-capacitors store much more electric energy than standard capacitors, they generally store orders of magnitude less electric energy than lithium-based batteries. Since there is no chemical reaction in ultracapacitors as found in batteries, ultra-capacitors charge and discharge their energy orders of magnitude faster than batteries. According to conventional technologies, the electrical storage performance comparison between batteries and ultracapacitors becomes a trade-off.

A need exists for systems/methods that overcome the inherent trade-off between storage capacity and discharge rate, as discussed above.

SUMMARY

The present disclosure provides an advantageous electrolysis treatment pursuant to which, in an aqueous (water) electrolyte bath condition, water (H₂O) is split at the outer and inner surfaces of the pores in the electrode to form hydrogen (H₂) gas and oxygen (O₂) gas that escape out of the carbonaceous electrode pores into the bath and expel loose materials (carbonaceous and other impurities) from inside the electrode pores outward. This outward escape of gas serves as a pore generation and pore expansion treatment, thus initially activating or further activating the electrode.

Furthermore, the ambiance of water electrolysis which produces the hydrogen, oxygen, and related solute molecular species (H₃O⁺, H⁺, OH^(−,) etc.) also kinetically react and electro-chemically react with materials of the carbonaceous electrodes, and remove undesirable compounds, thereby further activating the electrodes. The kinetically driven reactions and electrochemically driven reactions can be selectively controlled to remove undesirable materials from the electrode and not affect or minimally affect the base carbon structures and materials of the electrode by control of the voltage window applied in the disclosed treatment. Furthermore, these electrochemically driven and kinetically driven cleaning reactions can be controlled, enhanced and modified by addition of other solutes, salts, acids an bases in the electrolyte solution.

Additionally, the disclosed electrolysis treatment of the carbonaceous electrode grows advantageous nanostructures that are electrodeposited plating material on the surface of the electrode and in the channels and pores of the electrode which increase the surface area and therefore increases the energy storage capability when the electrodes are used in an electric double layer capacitor, ultracapacitor, pseudo-capacitor, battery or fuel cell as electrodes, or as any other adsorbing or adsorbing-desorbing function, or as electrodes in water-electrolysis based hydrogen gas and oxygen gas generators.

Additional features, functions and benefits of the disclosed systems and methods will be apparent from the description which follows.

BRIEF DESCRIPTION OF THE FIGURES

To assist those of ordinary skill in the art in making and using the disclosed systems/methods, reference is made to the accompanying figures, wherein:

FIGS. 1A thru 1D schematically depict an exemplary electrochemical setup according to the present disclosure;

FIGS. 2A-2B are SEM images of untreated versus treated carbonaceous biochar electrode wafers;

FIG. 3 provides four (4) SEM images depicting progressive magnification of the same area of the interior of an electrode treated by the electrolysis-activation method disclosed herein; and

FIG. 4 provides two (2) SEM images of the same area of an untreated monolithic carbonaceous biochar electrode under different magnification revealing the absence of preferential structures otherwise created by the disclosed method; and

FIG. 5 provides two (2) SEM images of the same area of the treated monolithic carbonaceous biochar electrode under different magnifications.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Discussion of the Figures:

With reference to the exemplary setup schematically depicted in FIG. 1A, the following components are identified as:

100: Overall apparatus setup for implementation of the disclosed methods for a single pair of electrodes being treated by Electro-Activation

105: The DC Power Source, hereinafter Power Supply (in an exemplary implementation, the DC Power Supply is a TekPower Model TP3005T DC Power Supply)

106: The Digital Display of Voltage output and Amperage Current output of the Power Supply (105)

107: The Voltage Output Adjustment of the Power Supply (105).

108: The Amperage Output Adjustment of the Power Supply (105).

109: The Positive Voltage Terminal of the Power Supply (105)

110: The Negative Voltage Terminal of the Power Supply (105)

111: Stimulus input to the Voltage Polarity Reversing Device (112); the stimulus can originate from within the Voltage Polarity Reversing Device (112) or be external to the Voltage Polarity Reversing Device (112)

112: A Voltage Polarity Reversing Device such that two distinct states of Direct Output Polarity and Reverse Output Polarity are possible when observing or measuring the device (112) output polarity terminals “A” and “B” relative to the device input polarity, and such device having a polarity switching activation caused by mechanical electrical stimulus (111), such as a timing device, such as manual manipulation. The output terminals of (112) are labeled A and B wherein, when the Voltage Polarity Reversing Device (112) is in the initial or resting state (unmanipulated by (111) or unstimulated by (111)) the “A” terminal provides the Positive Voltage Potential and the “B” Terminal provides the Negative Voltage Potential sourced from the DC Powe Supply (105). Furthermore, when the Voltage Polarity Reversing Device (112) is in the active state (manipulated by (111) or stimulated by (111)) and device (112) performs its Voltage Polarity Reversing function the “B” terminal provides the Positive Voltage Potential and the “A” Terminal provides the Negative Voltage Potential as sourced by the DC Power Supply (105).

115: A diagrammatic graphical zone delineating a specific area of the Overall Apparatus (100), wherein the delineated area is further amplified for detail and annotation in an expanded view, shown in the right-side area of (100) and wherein the zoom view area is depicted as (116).

116: The diagrammatic graphical area for expanded view and delineation providing further detail on the apparatus shown in (115). The details within (116) further depicting the Electrodes (150) and (151) and the Fastener Clips (125) and (135) as in the polarized state when the Voltage Polarity Reversing Device (112) is in the rest position and not stimulated by (111), thereby providing Positive Voltage to Fastener Clip (125) and Electrode (150), and Negative Voltage to Fastener (135) and Electrode (151).

120: The Positive Voltage Wire Conductor from the Power Supply (105) Positive Polarity Terminal (109) to the Positive Voltage Input of the Voltage Polarity Switching Device (112).

125: The “A” Voltage Electrically Conductive Fastener Clip of the Assembly holding the “A” Polarity Electrode (150). Observe that neither the Electrically Conductive Wire (120) nor the Electrically Conductive Fastener Clip (125) is in contact with the electrolyte (142),

130: The Negative Voltage Wire Conductor from the Power Supply (105) Negative Polarity Terminal (110) to the Negative Voltage Input of the Voltage Polarity Switching Device (112).

135: The “B” Voltage Electrically Conductive Fastener Clip of the Assembly holding the “B” Polarity Electrode (151). Observe that neither the Electrically Conductive Wire (130) nor the Electrically Conductive Fastener Clip (135) is in contact with the electrolyte (142),

140: The Electrolyte Bath Vessel made of non-electrically conductive material.

142: The Electrolyte Liquid in the Electrolysis Bath Vessel (140).

145: An Annotation of the basic electrochemical reaction of the electrolysis of water occurring between the electrodes (150) and (151) across the Electrolyte Liquid (142).

146: Negatively Charged Ions formed during Water Electrolysis (145) being attracted to the Positive Polarity Electrode herein depicted as (150), with the understanding that (150) is shown as the Positive Polarity Electrode due to the fact that the Voltage Polarity Reversing Device (112) is in the unstimulated state.

147: Positively Charged Ions formed during Water Electrolysis (145), being attracted to the Negative Polarity Electrode (151) with the understanding that (151) is shown as the Negative Polarity Electrode due to the fact that the Voltage Polarity Reversing Device (112) is in the unstimulated state.

150: The “A” Polarity Monolithic Biochar Electrode being subject to Electro-Activation in accordance with the disclosed embodiment.

151: The “B” Polarity Monolithic Biochar Electrode being subject to Electro-Activation in accordance with the disclosed embodiment.

Regarding FIG. 1B

With reference to the exemplary setup schematically depicted in FIG. 1B, the following components are identified as:

160: Overall apparatus setup for implementation of the disclosed methods for multiple pairs of electrodes (150), (151) being treated by Electro-Activation, each fastener clip being larger or longer than shown in FIG. 1A so as to hold more than one electrode of each polarity, with the limitation that only one fastener clip of each polarity “A”, “B” is used.

Regarding FIG. 1C

With reference to the exemplary setup schematically depicted in FIG. 1C, the following components are identified as:

180: Overall apparatus setup for implementation of the disclosed methods for multiple pairs of electrodes being treated by Electro-Activation, each fastener clip being larger or longer than shown in FIG. 1A so as to hold more than one electrode of each polarity, with the extension that a multiplicity fastener clips of each polarity is used, and wherein the arrangement of each parallel fastener clip is such that the assigned polarity alternates from one fastener clip rail to the next along the arrangement.

Regarding FIG. 1D

With reference to the exemplary setup schematically depicted in FIG. 1D, the following components are identified as:

190: Overall apparatus setup for implementation of the disclosed methods for a single pair of electrodes being treated by Electro-Activation, wherein the electrodes may be of significant size and weight such that the conductive fastener clips alone may not be sufficient to support and hold the electrodes submerged into the bath, thereby requiring an additional support (191).

191: An added support device of non-electrically conductive material providing mechanical support to the electrodes that are otherwise hanging from the conductive fastener clips, the addition of such supports (191) thereby preventing breakage of the electrodes due to gravimetric stress. Supports (191) are further connected to other external support devices (not shown) to assist in suspending the electrodes (150), (151) in the electrolyte bath (140).

With reference to the flowchart schematically depicted in FIGS. 2A and 2B, these figures show Scanning Electron Microscopy (herein after SEM) images of two similar electrodes, each being treated for activation by different methods disclosed herein.

Regarding FIG. 2A

200: Overall depiction of the SEM Image therein showing a magnified image of the surface and inner body of a Monolithic Carbonaceous Biochar Electrode material resulting from treatments disclosed herein. Image 200 shows the disclosed Carbonaceous Biochar Monolithic Wafers (210).

210: SEM image of the results of a Monolithic Carbonaceous Biochar Electrode material having been activated by common Steam-Carbon reaction having been treated in the High Temperature Furnace with the optional Steam-Activation step.

211: A graphical annotation highlighting the SEM screen image (210) showing a relative scale related to the screen image for a length dimension of 10 microns.

212: A datum from the SEM indicating on the SEM screen image (210) the magnification of the image of 1,320 times.

Regarding FIG. 2B

250: Reference 250 shows an SEM image of the disclosed Carbonaceous Biochar Monolithic Wafer (260). The overall depiction of the SEM Image therein shows a magnified image of the surface and inner body of the Monolithic Carbonaceous Biochar Electrode material resulting from treatments disclosed in this embodiment.

260: SEM image of the results of a Monolithic Carbonaceous Biochar Electrode material having been activated by the disclosed Electrolysis-Activation step. A distinct “Fuzzines” of the surfaces of 260 are evident versus 210 which shows no “Fuzziness”, such observable “fuzziness” being the growth of preferential nano- and micro-structures of carbon, specifically graphene and graphitic structures plated onto the monolithic biochar pore surfaces due to treatments by the disclosed methods.

261: A graphical annotation highlighting the SEM screen image (260) showing a relative scale related to the screen image for a length dimension of 10 microns.

262: A datum from the SEM indicating on the SEM screen image (260) the magnification of the image of 1,000 times.

Regarding FIG. 3, an electrolyzed carbonaceous monolithic biochar wafer electrode is provided showing growth of preferential graphene and graphitic structures for superior surface area improvement for dramatic increase in capacitance. These graphene and graphitic structures are caused by the treatments to the biochar due to the disclosed method.

300: The overall collection of four (4) SEM images depicting progressive magnification of the same area of the interior of an electrode treated by the Electrolysis-Activation method disclosed herein.

310: An SEM image of the inner structures of the pores and channels of the disclosed Monolithic Carbonaceous Biochar Electrode having been treated by the disclosed method, viewed at 1,000× magnification. Further, a graphical delineation (black box and arrow) indicating the zoom area for further magnification that is subsequently shown in 320. Further, a graphical delineation (black circle) highlighting the relative dimension of the SEM image on the SEM screen capture showing the reference length of 10 microns relative to the SEM screen image. Note that in image 310, the preferential graphene and graphitic self-assembled platelets and structures only appear as a fuzzy surface on the image of the treated biochar.

320: An SEM image of the inner structures of the pores and channels of the disclosed Monolithic Carbonaceous Biochar Electrode having been treated by the disclosed method, viewed at 5,000× magnification. Further, a graphical delineation (black box and arrow) indicating the zoom area for further magnification that is subsequently shown in 330. Further, a graphical delineation (black circle) highlighting the relative dimension of the SEM image on the SEM screen capture showing the reference length of 1 micron relative to the SEM screen image. Note that in image 320, the preferential graphene and graphitic self-assembled platelets and structures only appear as a fuzzy surface on the image of the treated biochar.

330: An SEM image of the inner structures of the pores and channels of the disclosed Monolithic Carbonaceous Biochar Electrode having been treated by the disclosed method, viewed at 20,000× magnification. Further, a graphical delineation (black box and arrow) indicating the zoom area for further magnification that is subsequently shown in 340. Further, a graphical delineation (black circle) highlighting the relative dimension of the SEM image on the SEM screen capture showing the reference length of 1 micron relative to the SEM screen image. Note that in image 330, the preferential graphene and graphitic self-assembled platelets and structures are clearly visible in the SEM image and can be identified on the surface of the treated biochar.

340: An SEM image of the inner structures of the pores and channels of the disclosed Monolithic Carbonaceous Biochar Electrode having been treated by the disclosed method, viewed at 84,740× magnification. Further, a graphical delineation (black circle) highlighting the relative dimension of the SEM image on the SEM screen capture showing the reference length of 100 nanometers relative to the SEM screen image. Note that in image 340, the preferential graphene and graphitic self-assembled platelets and structures are clearly visible and obvious in the SEM image and can be identified on the surface of the treated biochar. Furthermore, the image demonstrates that the carbonaceous structures that have plated out of solution during implementation of the disclosed method are thin and flat or curved platelets of single layer and few layer graphene, having been additionally tested by the Elemental Analysis Feature of the SEM system.

Regarding FIG. 4:

400: Reference for two SEM images (410) and (450) side by side of the same area of the untreated Monolithic Carbonaceous Biochar Electrode under different magnification.

410: An SEM image of the untreated the surface, pores and channels of the carbonaceous biochar material at magnification of 500×.

411: A graphical delineation (black circle) of the SEM screen image showing the dimension length relative to the screen image of 10 microns.

450: An SEM image of the untreated surface, pores and channels of the carbonaceous biochar material at magnification of 10,000×.

451: A graphical delineation (black circle) of the SEM screen image showing the dimension length relative to the screen image of 1 micron.

Regarding FIG. 5:

500: Reference for two SEM images (510) and (520) side by side of the same area of the treated Monolithic Carbonaceous Biochar Electrode under different magnification.

510: An SEM image of the preferentially grown and self-assembled iron flake and flower petal-like structures covering the surface, pores and channels of the carbonaceous biochar material.

511: A graphical delineation (black circle) of the SEM screen image showing the dimension length relative to the screen image of 1 micron.

512: A graphical delineation (black box) of the SEM screen image showing the magnification of 5,000×.

520: An SEM image of the preferentially grown and self-assembled iron flake and flower petal-like structures covering the surface, pores and channels of the carbonaceous biochar material at higher magnification than (510).

521: A graphical delineation (black circle) of the SEM screen image showing the dimension length relative to the screen image of 1 micron.

522: A graphical delineation (black box) of the SEM screen image showing the magnification of 20,000×.

General Summary of the Approach and Technique, including General Components:

-   -   A) The Components: The disclosed invention embodies a         carbonaceous free-standing wafer electrode of monolithic         structure, electrolyte solution, an electrolysis treatment bath,         electrical power supply, a polarity-reversing switching device,         and related wiring and fasteners, and optional ventilation.     -   B) The Process: The disclosed invention is described herein as,         inter alia, electrolysis treatment of the free-standing wafer         electrodes, electrochemical principles, and physical         arrangements.         -   Activated carbon, partially activated carbon, or             non-activated carbon electrodes, preferably with             hierarchical pores and channels, were synthesized using a             net-shaped technology as described in U.S. Pat. No.             9,478,324 and U.S. Pat. No. 10,121,563 to Favetta et al.,             and a contemporaneously filed provisional application             62/826,005 entitled “Process for Producing a Highly             Activated, Monolithic Net-Shaped Biomass Electrode for Use             in an Ultracapacitor, Pseudo-Capacitor, Battery or             Fuel-Cell” (the contents of which are hereby incorporated by             reference; collectively referred to as the “Favetta Patent             Filings”) and further activated using this disclosed process             herein, in an electrolytic bath under applied electric field             of a controlled voltage potential (V) and direct current             (DC).         -   The conductive carbonaceous monolithic biochar electrodes             were each attached to separate current conducting fastener             and submerged into an aqueous salt electrolyte bath with an             applied electric field above 1.27 Volts, wherein water             electrolysis begins and, more specifically, above the             minimum approximate 1.65 volts or minimum 1.70 volts, where             hydrogen and oxygen gas generation begins and continues             through higher voltage profiles. Only the electrode material             was submerged into the aqueous electrolyte solution and             wetted, but not the current conductors, nor the metallic             fasteners, clips nor wiring, to prevent a short circuit in             the system via the exposed metal of thes fasteners, into and             through the conductive electrolyte solution.         -   The electrically conductive electrodes at the applied             voltage potential enabled the splitting of water to form             gaseous hydrogen (H₂) and oxygen (O₂) at the cathode and             anode carbonaceous electrodes, respectively. These generated             and expelled gases, and the electrochemical and kinetic             reactions occurring in the pores of the electrode are             particularly advantageous.

Electrolyte Bath Description

-   -   A highly concentrated salt solution electrolyte of aqueous         potassium hydroxide (KOH) in distilled water of concentrations         such as 4 to 5 Molar, such as 5 to 6 Molar, or such as 6 to 7         Molar, was prepared and used as the environment for the         electrolysis activation bath. Pairs of partially activated         carbonaceous monolithic biochar electrodes were clamped with         commercially available electrically conductive fasteners, such         as alligator clips, that included adding a layer of thin (0.004         inches thickness) of 316 stainless steel foils as current         conductor plates actually touching the electrodes to avoid         having the alligator clips from biting and damaging the         monolithic carbonaceous electrodes, and such foils further         increasing surface area of contact between the conductors and         part of each monolithic carbonaceous electrode wafer, and such         electrically conductive fasteners which were connected by         insulated copper wire to a power supply (105) and a time/cycle         relay (112) (see FIG. 1).     -   The electrical current conductor clips can be titanium, aluminum         or stainless steel, or any other electrically conductive         material, subject to maintaining the DC electric current flow         through the system which can otherwise be inhibited by some         corrosion/oxidation of the metal conductor fasteners, parts,         clips and foils, caused by these metal parts' proximity to the         electrolyte solute/salts and flowing electric current of the         disclosed arrangement of the embodiment. Furthermore, it is         advised that these electrical current conducting fasteners,         foils, plates and clips should be periodically maintained,         sanded, polished and cleaned as corrosion forms on them which         causes electrical resistance. While the monolithic electrodes         are submerged in the electrolyte bath for the disclosed         electrolysis activation, it is highly recommended to cycle the         polarity of the voltage potential applied to the electrode pairs         so as to allow for equal and consistent electrolytic activation         on both electrodes. This is embodied herein as shown in FIGS.         1A-1D as the Voltage Polarity Reversing Device (112). This         cyclical voltage reversal as applied to the electrodes         promulgates the related gaseous expulsion and electrochemical         reactions in both polarity directions across the electrode pairs         more equally; however, under certain specific embodiments of the         invention, certain other beneficial effects to the electrodes         can be derived if each electrode of the pair is set to be         treated at only one polarity, without such polarity cyclical         reversals.     -   Cycle times are also a function of actual voltage potential         applied, and resulting current flows (DC Specific Power), or         overall cumulative Specific Energy Flow, as the case may be for         the varied desired end results of activation and end use of the         electrode/carbonaceous materials. Successful cycle times         include, but are not limited to, between 2 to 4 minutes per         polarity, then reversing the voltage polarity and current flow         across the electrode pair for an additional 2 to 4 minutes,         thereby undergoing one voltage reversal cycle, and performing         this positive-negative DC voltage reversal cycle 3 to 5 such         complete cycles at a minimum of more than 2.0 Volts DC to no         more than 5.5 Volts DC as measured at the electrode connection         point, thus excluding voltage potential losses and voltage drops         across any supporting or connective devices, such as electrical         wiring and electrode fasteners, clamps, foils and clips.

Discussion of Cleaning Action/Gas Generation Caused by the Electrolysis Bath Treatment of the Invention.

-   -   When an electric voltage potential of 1.23 Volts or more is         applied to water that is electrically conductive due to the         presence of free ions, such as via addition of an electrolyte         salt, base or acid, an electric current passes through the water         solution and the electric current breaks down the water molecule         (H₂O) into hydrogen ions (H⁺F) and hydroxyl ions (OH⁻). As the         voltage potential between the electrodes is increased to         approximately 1.65 Volts to 1.7 Volts, the hydrogen ions combine         and form hydrogen gas (H₂). Simultaneously, at these voltage         conditions the disassociated hydroxyl ions reform, further         disassociate and recombine and form oxygen gas (O₂). These (H₂)         and (O₂) gas molecules agglomerate to form hydrogen gas bubbles         and oxygen gas bubbles respectively. This process of water         hydrolysis and generation of hydrogen gas and oxygen gas by an         applied electric potential and resulting electric current is         commonly understood. To form such solution, the electrical         conductivity of the water is enhanced by adding a disassociating         salt, acid or base, thereby creating a solution of conductive         ions such as an electrolyte. The salt can be any such         water-soluble salt; however, the concentration of the salt must         be adequate to effectuate the desired results, and the ion         components of the salt must provide the selectivity of the         desired electrode activation and resultant by-product formation.     -   Furthermore, if material plating onto the carbonaceous electrode         scaffolding within the channels and pores of the electrode is         also desired, the ionic compounds must either effectuate such         deposition or not inhibit such deposition if other compounds are         added to the electrolyte bath solution to separately effectuate         this optional desired material plating into the electrode pores.     -   Exemplary embodiments herein use salts, such as the stated 6         Molar potassium hydroxide (aqueous). The positively and         negatively charged free radicals and ions are attracted to the         cathode and anode surfaces, respectively, where         electron-transfer takes place, and can recombine to form         hydrogen (H₂) and oxygen (O₂) gas on the negative potential         cathode electrode and positive potential anode electrode         respectively.     -   The free radicals, electrolyzed organic compounds and formed         gases also accumulate on the surface of the electrodes as well         as inside the pores and channels of the porous electrodes. Upon         reaching a critical bubble size, the low density of the         expanding gas bubbles causes them to grow and expel outward from         the electrode pores and surfaces and upward towards the surface         of the aqueous bath electrolyte solution. These expulsions of         gaseous vapor carry along with them the loose particles of         oxidized contaminants trapped within the internal pores and         channels of the activated electrode, which provides a mechanical         and chemical cleansing effect and provides a first level of         electrolysis activation.     -   Additionally, these expanding gases also expel the mixture of         aqueous electrolyte solution and other organic compounds of many         varied organic moieties found within the electrode (originally         formed during the prior and independent charring of the source         biomass—see Favetta provisional application: Serial No.         62/826,005) that are undesirable and reside at the electrode         pores' surfaces, such moieties having a detrimental effect on         the electrodes performance when used in a battery,         ultracapacitor, pseudo-capacitor or fuel cell. These moieties         may not necessarily be free-standing particles or solutes nor         simply residing as loose particles in the pores of the         electrodes. These moieties may furthermore be chemical         functional groups that are chemically bound to the high purity         carbonaceous structures of the electrode. In all such cases         these moieties and compounds are removed from their bound         chemical adhesion from the electrode pore walls by         electrochemical breakdown from the disclosed treatment, into         solution or suspension, then carried out of the electrode pores         by the gaseous driven conveyance of the liquid solution as         described herein. If such removed and disassociated moieties are         charged ions or free radicals, they may be additionally driven         into the solution electrolyte bath by electrochemical potential         of the applied voltage.     -   Furthermore, such moieties have a voltage window of their own         electrolysis below that of the more pure and structured         carbonaceous scaffolding of the desirable electrode material,         which in turn results in a cleansing effect of the electrodes'         channels and pores. This electrochemical “scrubbing” of the         electrodes' pore walls is a second level of activation of the         electrodes effectuated by the disclosed invention.     -   This cleansing and expulsion of contaminants is evidenced by the         severe darkening coloration of the aqueous electrolyte solution         bath after multiple electrolytic cyclical alternating DC voltage         potential cycles. Typical coloration of the electrolyte bath         solution is that of an oxidized organic substance of brown         color. Some coloration of the electrolyte bath is observable in         the first cycle of electric potential application.     -   The cleansing of the internal pores and channels further         increases the active and usable total surface area of the carbon         electrodes thereby greatly increasing the electrical and         chemical absorbency of the electrode material end product.     -   An example of the improvement in performance of the same         electrode material prior to electrolysis treatment and after the         disclosed electrolysis treatment is 3 to 4-fold, and as much as         20-fold in some cases when tested in an ultracapacitor         application. This results in an increase from nominal 10 to 40         Farads per gram for the untreated electrodes to upwards of 150         to 300 Farads per gram for the same electrodes after         electrolysis treatment by the disclosed method.     -   Additionally, the electrolytically and kinetically generated         free-radicals in the pores and channels within the electrode         also electrochemically react with certain less stable organic         compounds within the electrodes at the carbon walls of the pores         and channels and on the surfaces to then dissolve and remove         undesirable organic compounds such as tars, oligomers,         polysaccharides and simple sugars that can be formed when the         electrode is made of biomass-sourced materials. Such reaction         by-products are likewise expelled out from the pores and into         the surrounding aqueous solution, further coloring the aqueous         electrolyte bath solution with brown organic solute and         suspensions.

Growth of Carbon-Based Nanostructures (Graphene, Several-Layer Graphene, Graphitic Platelets, and the Like)

-   -   The growth of carbon-based nanostructures is caused by the         “release” of some carbon-containing oxidized and electrolyzed         molecules or particles into the electrolyte bath solution by the         electrolysis “off-gassing” of the disassociated water molecules         in the bath solution and the “plating growth” of new carbon         structures on the cathode and anode electrodes. The source of         the carbon compounds for this carbonaceous plating and growth         effect are from these carbonic compounds being transported back         into the electrode pores and channels by the surrounding aqueous         solution containing these carbonaceous organic moieties and by         their ionic charge in the voltage potential that exists between         the oppositely polarized electrodes.     -   Additionally, some carbonaceous chemical species transport no         further than locally at the carbonaceous walls of the electrode         pores and react with insipient electrolyte within the pores and         reduce and plate-out or crystallize directly back onto the pore         walls to form advantageous structures such as graphene and         graphitic dendrites, thereby increasing surface area,         conductivity and significantly increasing electric storage         capability of the electrodes when treated by the disclosed         method. These other side-reactions of the organic compounds in         the carbonaceous electrode that react with the free-radicals         generated in the electrochemistry of the system further supply         carbon species that are then reduced back onto the inner wall         surfaces of the electrode pores and channels, forming         graphene-like structures and dendrites to greatly increase         surface area and conductivity of the electrochemically activated         final electrode item.     -   Under controlled conditions of electrolysis activation, it was         noted that growth of “new” carbonaceous structure was observed         using a scanning electron microscopy (SEM). This plating of new         carbon material resulted from the mobility/migration of the         loose carbon-based particles as well as disassociated carbonic         free radicals being reduced onto active carbonaceous sites of         the electrode's pores, inner walls and surfaces.         Plating/Growth of other Materials, such as Metals, via the use         of a Counter-Electrode, or Metallic-Containing Salts, introduced         into the Aqueous Solution during Electrolysis can be Performed.     -   Such inclusions of metallic compounds and structures may require         adjustment in the power supply DC voltage to account for the         required galvanic potential and half-cell potential of the metal         and a second potential voltage control of the counter-electrode         itself, to properly control the contribution of this         counter-electrode in the process of plating and forming of         advantageous structures within the pores and surfaces of the         treated electrodes according to the disclosed invention.     -   It is noted herein that a non-carbonaceous (metallic) counter         electrode can be sacrificially used to electroplate the inner         pores, channels and walls of the carbon electrode (i.e.,         transfer and deposit metallic atoms from one metallic         counter-electrode to the target carbon electrode). The electric         current and voltage different potential of the counter electrode         drives charged atomic particles or ionic moieties from the         surface of the counter electrode onto the surface of the target         carbon electrode thereby growing a thin and localized plating of         metallic moieties and structures on and within the pores of the         carbon electrode. This may have an advantageous and phenomenal         effect for the plated-carbon electrodes depending on the         targeted application (e.g., electrochemistry,         pseudo-capacitance, catalysis, etc.).     -   The disclosed method was used to plate iron, manganese and other         metals onto the inner pore surfaces of the electrode. Results         demonstrated improvements in electric storage performance of the         electrodes. Other absorbency and desorbency effects of the         electrode by this metallic deposition method, and other         applications such as agriculture, chemical adsorption,         catalysis, waste purification, waste absorbency, gas or liquid         storage such as hydrogen, such as natural gas (methane), such as         fuel, such as radioactive contaminants of mineral and petroleum         recovery from geological fracturing (fracking) are further         contemplated according to the present disclosure.         Use of Alternative Electrolyte Solutions besides Alkaline         KOH(aq), NaOH(aq), etc.     -   Alkaline compound electrolytes (containing OH⁻ ion species) in         the bath solution serve to conduct electricity to facilitate the         water electrolysis, but also play a role in the electrochemistry         at the electrode surfaces to catalyze the disclosed effects to         generate organic free radicals. The presence of other         non-alkaline electrolyte ion species furthermore facilitates the         reduction of these organic or metallic moieties to deposit and         plate onto the pore and channel surfaces within the electrode,         thereby greatly enhancing the properties and performance of         these electrolysis treated electrodes for superior conductivity,         and capacitive and pseudocapacitive performance.

Increased Capacitance of Treated Materials.

-   -   The treated electrodes (monolithic biochar wafers) generally         increased in faradaic capacitance by 20% to 300%, and in some         cases approximately 2,000%. Monolithic untreated biochar         electrodes prior to being treated by the disclosed methods         herein, and produced by the methods disclosed in the Favetta         Patent Filings (incorporated by reference hereinabove) exhibit         desirable electric capacitance such as 50 to 90 Farads/gram,         such as 90 to 120 Farads/gram, such as 120 to 140 Farads/gram,         and such as above 140 Farads/gram, depending on formulation and         embodiments of the production processes utilized as further         descried in the Favetta patent filings.

These are very desirable results. After electrolysis treatment by the disclosed methods and systems herein, the same treated electrodes exhibit over 150 Farads/gram and up to 300 Farads/gram when used in an ultra-capacitor.

Description of Net-Shaped Wafer Process

-   -   Highly porous activated monolithic carbon electrodes with         hierarchical pore structure were synthesized using the         net-shaping process followed by high temperature charring with         optional simultaneous chemical activation or optional         post-charring chemical activation, as described in the Favetta         Patent Filings (previously incorporated by reference).

Importance of Surface Area to Capacitance

-   -   The faradaic capacitance of the ultracapacitor is proportional         to the surface area of the electrode and inversely proportional         to the spacing between the electrodes; however, the relationship         of capacitance and surface area is not necessarily purely         linear. The disclosed process delivers an increase to the         internal surface area of the electrode through multiple         activation steps (such as high temperature chemical activation)         and/or the disclosed electrolysis as described herein to         optimize the surface area without compromising the structural         integrity, mechanical stability, and underlying chemical         properties of the carbonaceous biochar monolithic electrode         wafer.

Exemplary Process Implementations

-   -   An exemplary disclosed electrochemical apparatus consists of a         solvent bath of a conducting electrolyte such as 4 to 8 Molar         potassium hydroxide (KOH), such as 1 to 3 Molar sulfuric acid         (H₂SO₄), or such as a neutral salt such as 4 to 7 Molar         potassium chloride (KCl). Additionally, the electrolyte in the         bath can be a metal salt, such as iron nitrate (Fe(NO₃)₃) or         such as iron hydroxide (Fe(OH)₂) or a manganese salt such as         manganese chloride (MnCl₂), the species and concentrations of         which depend on the particular metal desired to be plated onto         and into the electrode and the total amount of such metal to be         deposited on and within the electrode for increased properties,         such as increased capacitance due to the iron or manganese based         pseudo-capacitance.     -   The monolithic electrodes made of biochar, to be activated via         this disclosed method can optionally be pre-treated to remove         air/gas from the pores and pre-soak in this electrolyte with the         aid of ultrasonication, or applied vacuum and subsequent         re-pressurization while submerged in the electrolyte solution,         in order to remove incipient gas from the pores and fully wet as         much of the interior pore structure as possible. Note, however,         this pre-soaking/impregnation is not required, but expedites the         overall process by pre-wetting the internal pores of the         electrode rather than waiting for the diffusion of the         electrolyte into the pores to occur while the voltage potential         is applied, which has been observed to take up to several         minutes at the beginning of the first electrolysis cycle of         applied voltage potential.     -   Additionally, the counter electrode described in the sections         above can be made of a sacrificial metal which will then be         plated onto and into the biochar electrode pores and surfaces         during the electrolytic treatment as disclosed herein. The         electrodes to be activated are then placed in the electrolyte         solution bath as close as possible to each other without         touching each other.     -   It is necessary that the oppositely polarized electrodes do not         touch each other.

This can be accomplished with the aid of an electrically insulating, porous separator to minimize this space between the electrodes and prevent electrode-to-electrode contact. Embodiments of such porous non-conducting separators can include a simple sponge or open-cell polymer foam rubber, porous plastic film, woven or non-woven cloth of polymer fiber, ceramic fiber, or silica-based fibers such as glass wool insulation and the like.

-   -   In exemplary embodiments of the disclosed invention, the         distance between the electrodes was approximately 1 centimeter         and these flat planar electrodes were maintained as parallel to         each other as possible, to within about 10 to 15 degrees angle         of the planes. The electrodes are held with conductive         (preferably non-corroding) clamping device, such as alligator         clips or any other simple clamping and fastening method or         means, by a tab of electrically conductive material. All         electrically conductive fastening and clamping parts other than         the carbonaceous electrodes themselves are kept out of the         conductive electrolyte solvent bath to avoid an electrical short         circuit and to ensure electric current conduction only through         the electrode material submerged in the bath and not via a         short-circuit through the electrically conductive fasteners,         clips, foils and metal holders into the electrically conductive         electrolyte solvent bath. The electrically conductive fasteners,         clips, foils and holders, such as alligator clips, such as         spring clamps, such as weighted clamps, are then connected by         wires to a direct current (DC) power supply. See 100 (FIG. 1A to         FIG. 1D).     -   The DC power supply is then adjusted to a potential sufficient         to activate the electrodes for the desired end result with a         minimum of more than 1.7 Volts in order to hydrolyze (split)         water. This voltage is also high enough to generate gaseous         bubbles of hydrogen (H₂) and oxygen (O₂) on all surfaces of the         monolithic wafer carbonaceous electrode including gas generation         internal to the monolithic electrode body, in channels and         pores. As these gas bubbles escape, they purge and transport out         loose carbon, contaminants and ash particulates that were         clogging the pores and channels of the electrode. Additionally,         some micro and nano-structures of carbon that had been formed in         the biochar electrode are further activated within the         electrodes. Due to electrochemistry effects, some of the         carbonaceous compounds that are loosened and transport into the         liquid bath themselves additionally undergo electrochemical         reactions with the biochar pore walls, and undergo chemical         reduction into pure or near-pure carbon, thereby growing as         platelets of ordered carbon structures, such as graphene, such         as graphitic structures. Higher voltage and currents produce         more aggressive bubbling and increase the rate at which         activation, purging and graphene and graphitic growth occurs.     -   It should be noted that since basically all materials have a         breakdown voltage, the maximum applied voltage should remain         below such potential level to avoid disintegration of the         electrode or its binder material or self-binding materials.     -   Additionally, higher voltages may be necessary to electrolyze         certain carbonic moieties of the biochar that were disassociated         from the biochar electrode, into solution, and then reduced,         deposited or plated back into the carbonaceous biochar         electrodes from the electrolyte solution or from carbonic ions         introduced as salts or organic liquids into the electrolyte         bath. Additionally, higher voltages may be necessary to plate         certain metals into the carbonaceous biochar electrodes from the         metallic counter electrode or from metallic ions introduced as         salts into the electrolyte baths. The higher voltages up to 5.5         V can be utilized for this metallic electrochemical method as         needed depending on the overpotential necessary to overcome         resistances in the wiring and within the electrode itself. This         “suggested” 5.5 Volts of potential between the electrodes         unfortunately is near the breakdown voltage of much of the         carbon structures in typical biochar carbonaceous electrodes         such as those formed from biomass, hence caution should be taken         when optimizing deposition rates and activations rates versus         the limits of the breakdown voltages of the electrode material         itself.         Description of Superior Properties Gained from Activation of Two         Monolithic Biochar Electrode Wafers     -   The post-charring activated carbon electrodes provided by other         upstream methods (as described in the Favetta Patent Filings;         previously incorporated by reference) may exhibit hydrophobic         behaviors upon initial contact with an aqueous electrolyte         solution when applying the methods of the invention disclosed         herein. This typically results from incomplete charring and         activation in prior steps or prior applied activation methods         (see Favetta Patent Filings) which then results in less creation         of the heat-produced micro and nano pores within the electrode         or can be cause by obstructed pores within the electrodes or on         the surface of the electrodes, from the byproduct of charring         that can cover the surface of the electrode and cover the walls         of the inner pores and channels of the electrodes during         charring (see Favetta, et. al. provisional Ser. No. 62/826,005).         Such undesirable charring byproducts can include tars,         oligomers, and sugars such as polysaccharides.     -   However, the electrolysis treatment disclosed herein allows for         the aqueous electrolyte solution to percolate into the internal         structure of the electrode to then be catalyzed, oxidized, and         reacted, thereby expelling the produced gases outward and         widening the pores and removing any charring byproduct coatings.         It was evidenced that the post-electrolysis wafers were more         hydrophilic than the pre-electrolysis electrode wafers.         Additionally, the opening and widening of the pores allowed for         faster and more accessibility of the electrolytes (less         diffusion resistance) and demonstrated significant improvement         in capacitance, pseudo-capacitance, battery charge and discharge         rates, and overall energy density and power density improvements         of these assembled devices, as well as fuel-cell electrode         volumetric efficiency and space-velocity.

Although the present disclosure has been described with reference to exemplary embodiments and implementations thereof, the present disclosure is not limited by or to such exemplary embodiments/implementations. Rather, the systems/methods of the present disclosure are susceptible to modifications, variations and refinements that will be apparent to persons skilled in the art based on the disclosure provided herein, and the present disclosure encompasses such modifications, variations and refinements. 

1. A method comprising: applying an electrochemical treatment of electrolysis to monolithic electrodes made from monolithic biochar wafers, thereby modifying desired properties of the monolithic biochar wafers.
 2. The method according to claim 1, wherein an applied electric potential greater than 1.7 V is used to activate monolithic electrodes made from biochar wafers clamped to current conducting fasteners, and said biochar wafers are submerged into an electrolyte bath.
 3. The method according to claim 2, wherein the applied electric potential and resultant electric current through the electrodes is effective to cause the electrolysis of water in the electrolyte bath.
 4. The method according to claim 3, wherein electrolysis of water on and within the submerged carbonaceous biochar electrodes submerged in the electrolyte bath generates free radicals and gases on the surface of, and within the pores of, the monolithic carbonaceous biochar electrode.
 5. The method according to claim 4, wherein the generated gases form gas bubbles.
 6. The method according to claim 5, wherein the gas bubbles expand within the pores and on the surface of the biochar electrode and escape, pushing out, conveying out and transporting out other contaminants, particles and moieties existing in the pores of the carbonaceous biochar electrode and thereby cause removal of undesirable elements or material and/or further opens the pores of the electrode porous material causing additional electrode activation of the subject monolithic carbonaceous biochar electrodes.
 7. The method according to claim 1, wherein the electrolysis treatment is used for electrochemical reactions and gaseous cleaning of pores and removal of undesirable material including at least one of tars, oils, sugars, polysaccharides and other impurities from the biochar electrodes.
 8. The method according to claim 1, further comprising providing a co-solvent, a co-solute electrolyte or a combination of a co-solvent and a co-solute electrolyte, wherein the co-solvent and the co-solute electrolyte are selected from the group consisting of glycols, alcohols, aqueous potassium hydroxide, aqueous sulfuric acid, aqueous potassium chloride or combinations thereof, to enable at least one of graphene/graphite growth and deposition and plating on surfaces and within pores of the monolithic carbonaceous biochar electrodes of graphene and graphitic materials.
 9. The method according to claim 8, wherein the sources of the carbon for the growth of graphene and graphitic structures on and within the surfaces, channels and pores of the carbonaceous biochar electrodes originates from the free-radical carbon moieties.
 10. The method according to claim 1, further comprising providing a counter-electrode of carbonaceous or non-carbonaceous structure and wherein the counter-electrode is used to assist the growth of graphene/graphite-like material under applied electric field, and said material is plated onto the electrode pores, channel walls and surfaces.
 11. The method according to claim 1, wherein a metallic counter electrode is used for plating/growth of nanostructures on the surface and interior pores of the electrodes by metals in the solvent bath to improve the materials properties.
 12. The method according to claim 2, wherein the applied electric voltage polarity of the electrodes is cycled every 2 to 4 minutes per polarity for two or more cycles.
 13. The method according to claim 1, wherein the post-treatment monolithic biochar wafers exhibit an increase in capacitance, pseudo-capacitance and/or energy storage ability from the aforementioned treatments with applied electric voltage potential field and electrolysis embodiments.
 14. The method according to claim 1, wherein the electrolytically treated electrode is rinsed and dried for use in an aqueous application.
 15. The method according to claim 1, wherein the electrolytically treated electrode is rinsed and dried for use in a non-aqueous application.
 16. The method according to claim 15, wherein the non-aqueous application is selected from the group consisting of ultra-capacitors using organic solvents.
 17. The method according to claim 16, wherein the organic solvent is selected from propylene carbonate and acetonitrile.
 18. The method according to claim 15, further comprising one or more dissolved salts.
 19. The method according to claim 18, wherein the one or more dissolved salts are selected from tetra-fluoro-borates, hexa-fluouro-phosphates, ionic liquids, pyrrolidinium compounds, imidazolium compounds, BIS(triflouromethylsulfone)amides and a combination or moiety thereof.
 20. The method according to claim 1, wherein the electrodes treated by the disclosed method have advantageous performance improvements when applied to use in an ultra-capacitor, pseudo-capacitor, battery or fuel cell, or other absorbent and/or desorbing applications. 